Abstract
Ferroelectric oxides PbZr(1-x)Ti(x)O(3) (PZT) with the ABO(3) perovskite structure exhibit exceptional polarization responses near their morphotropic phase boundary (MPB), yet the chemical origin of this behavior remains unclear. Here, we show that, in a prototypical composition, 0.05Pb(Mn(1/3)Sb(2/3))O(3)-0.95PbZr(0.52)Ti(0.48)O(3), this origin arises from coupled effects of B-site chemical ordering and multi-ion displacement heterogeneity-related disordering. Pronounced anti-self-clustering of Zr and Ti forms a short-range chemical ordering driven by the mismatch between ionic Zr-O and more covalent Ti-O bonds, generating a soft-hard compatible BO(6) network that reduces local stress, which facilitates polarization rotation and switching. Simultaneously, A-site, B-site, and oxygen ions display significant, directionally distinct off-center displacements, producing continuous local monoclinic polar states (M(A)-M(B)) with coplanar polarization vectors and nanoscale domains with mobile walls. These results show that PZT's extraordinary response emerges from a unity-of-opposites relationship that balances rigidity and flexibility through compatible bonding and multi-ion displacements, offering guidance for designing high-performance ferroelectrics.